Production of solid contact material



J. R. BATES HAL 2,412,95

YRODUC'ION OF SOLID CONTACT MATERIAL Dec. 24, 1946. J, R, BATES TAL 2,412,95

' PRODUCTION 0F SOLID CONTACT MATERIAVL Filed Jan. 25, 1942 :s sheets-sheet 2 MIXING HEAO INVENTOR JOHN R. BTES HUERT A. SHABKER AT1-ome: l

Dec. 24, 1946. J. R. BATES ETAL PRODUCTION OF SOLID CONTACT MATERIAL Filed Jan. 23, 1942 3 Sheets-Sheet 3 ,/xNvENToR f,

'l JOHN R. BATES v HUBERT/1 sima/)frm ATTORNEY PRODUCTION or soLm coureur MATER John R. Bates, Swarthmore, and Hubert A.

Shabaker, Media, Pa., assignors to Houdry llrocess Corporation, Wilmington, Del., a corporation of Delaware l Application Illanuary 23, 1942, Serial No. 427,918y

4 Claims. (Cl. 252-254) 2 This invention relates to processes for producample, the gel must be sufciently aged to peling solids having desired physical and chemical let and at the same time be sumciently dense to properties and resulting from the interaction of settle in the Washing operation as for example, solutions. More particularly, it has to do with in a Dorr thickener or classier. The present commercial or large scale production of gels and 5 invention rests upon the discovery that this can gelatinous precipitates and the treatment and be done by mixing together two gaseous compoconversion of the same into forms suitable for nents to provide a treating medium for the gel ultimate use. It involves both process and appaso as to quickly reach the proper aging temperan ratus aspects. ture. One of these'components is -a condensable Aging of a gel following its initial formation gas and the other is a non-condensable gas. The has, in many instances, much to d0 with its submaximum temperature obtainable is that equal to sequent characteristics. In fact, without proper the temperature at which the liquid of the liquid aging, a gel frequently will not have the desired phase of the condensable gas reaches the partial density or porosity, will have a tendency to dispressure lof the condensable gas leaving the geil integrate into powder when stability in lump o1; 15 after contacting or passing through it. For granular form is needed, will be incapable of beample, if a mixture of air and steam is used ing molded into stable pellet form by extrusion or treat the gel, the ratio of air to steam will deter" casting for catalytic or other contacting operamine the maximum temperature which can tions, etc. The simplest method of effecting aging reached by a condensation of steam 'from the is to let the gel or gelatinous precipitate stand at go mixture. a fty-fty mixture 0f all' and steers. room temperature for the required length of is passed through a gel, the maximum temperatime, which will vary from a few hours to several ture which may be obtained would be that of lic;` days or even longer, depending upon the type or uid water at a half atmosphere vapor pressure or composition of the gel or upon the extent of mcdapproximately 178 F. Actuallyy it is lower ication necessary to bring out the desired prop- 25 this, since in practice whatever condensation oc-4 erties. It has been proposed heretofore to decurs to increase the temperature of the gel crease the density of gels by the use of heat, by creases the partial pressure of the water in the immersing gels in hot water, etc. steam air mixture. Since a maximum tempera One object of the present invention is to imture is .set by the composition of the mixture, .loL1

prove the technique of large scale manufacture of cal overheating, as will occur with steam alone. synthetic gels. Another object is to effect the is prevented, and temperature gradients are .ie- 1 manufacture of such gels in a continuous manby reason of the lower maximum temperature ner, Another object is to control the nature and and the large amounts of fluid passing over or extent of the aging treatment without requirthrough the gel. By varying the ratio of steam ing excessive equipment or delaying or interruptto air any temperature up to the boiling point of ing continuous manufacture of gel. Another obwater may be obtained in a. controlled manner. ject is to devise apparatus for carrying out the This gives a controlled aging to the gel which has above objects. Still other objects will be apparbeen found to be necessary to produce a gel which ent from the detailed description which follows. will pellet to give formed pieces of satisfactory The aging operation should b e conducted so as hardness and which will at the same time settle t0 reduce the density 110i? Only 0f the Subsequent satisfactorily in the washing procedure. In pracn dry gel but also of the gel after it has been tice the steam may be used to pump the necessary washed. In the washing operation it is usually amount of air into a combined stream by means necessary for the particles of gel to settle out of of a pump or ejector, or each fluid may be fed the washing water and out of the various agents under pressure individually into a mixing chain-- which may be used to treat the sel during 0r prior ber. thence into Contact with the body of the gel. to the washing operation. If the aging operation In order to illustrate the invention the is carried out to too great an extent the settling manner of its use, concrete forms of apparatus characteristics of the gel particles are usually imare shown in the accompanying drawings, paired and difliculty is experienced in obtaining which:

a suitable Washing operation. In this event, and Fig. l is a side elevational view, partly cut away for the gels showing this phenomenon it is necand in section, of equipment for gel production; essary to regulate the amount of aging within Fig. 21s a tcp plan view of the apparatus shown certain narrow limits. In other Words, in the in Fig. l with the casingremoved; production of synthetic contact material, for ex- Fig. 3 is a transverse sectional View substan tially on line 3-3 of Fig. 1 showing idlers supporting the upper run of the main conveyor'belt;

Fig. 4 is an enlarged cross sectional view of two of the distributing pipes for the treatingr fluid;

Figs. 5 and 5a are respectively a fragmentary side elevational view and an end elevational view of a mixing head equipped with a gel cutting device;

' Fig. 6 is a fragmentary side elevational view partly in section of another belt conveyor and distributing arrangement for the treating fluid;

Fig. 7 is a transverse sectional view on the line 1 1 of Fig. 6;

Fig. 8 is a fragmentary diagrammatic showing of another belt arrangement sectioned longitudinally of the belt;

Fig. 9 is a vertical sectional view of another modification of the invention;

Fig. 10 is a longitudinal sectional view of still another modication of the invention;

Fig. 11 is a horizontal sectional view on the line II---II of Fig. 10; and

Fig. 12 is a transverse sectional view on the line I2-I2 of Fig. 10 showing a. modication thereof.

Figs. 1 and 2 illustrate somewhat diagrammatically commercial equipment for producing gelsv on a large scale. In the form shown the reactants which combine to form the gel are fed to a mixing head I3 of any suitable or desired type producing substantially instantaneous formation of gel which issues in solid form from the lower-end of the head as indicated. Suitable equipment of this type is disclosed in the copending application of H. A. Shabaker, Serial No. 398,731, filed June 19, 1941 (now Patent No. 2,370,200, issued February 27, 1945). There may be any number of connections for reactants to the mixing head, three being shown at I4, I5 and I6. In a typical operation to make silicaalumina gel, for example, sodium silicate solu- .tion may be fed through line I4, sodium aluminate solution by line I5, the solutions being thoroughly mixed in the head, and a coagulating agent, such as ammonium sulphate or ammonium chloride solution. being added through line IB to produce instantaneous gel formation.

The mixing head is preferably provided at its delivery end with a cutter I1, shown on a larger scale in Figs. 5 and 5a, for the purpose of cutting and breaking the gel up into pieces or chunks of suitable size. The cutter illustrated takes the form of an annulus Ila partly telescopedover the exterior of the delivery end of mixing head I3 and rigidly held on the same by machine screws I'Ib, the annulus having cutting wires IIc extending across the open end of the mixing head. The pieces of gel falling from head I3 are directed by guide I8 to a distributing belt I9 pivoted below the mixing head and arranged to oscillate (by means not shown), as indicated by the arced double-headed arrow in Fig. 2, over a broad main conveyor' belt 20 of rubber or ilexible material. The oscillating belt I9 distributes the gel pieces in an even layer several inches deep across conveyor belt 20, the pieces piling up around and over a. series of equally spaced perforated pipes 2l extending just above conveyor belt 20 4and for a portion of the length of the latter. The perforations in the pipes 2l are directed downwardly as indicated in Fig. 4 and discharge the treating fluid or medium, preferably a mixture of steam and air, under pressure into and through the heaped up pieces of gel as conveyor belt 2li drags the gel upwardly belt 20 moves slowly lso that the heaped up gel is retained thereon for an appreciable length of time, as from ten minutes to two hours depending upon the desired amount of hot aging required, the gel being kept from bouncing off belt 20 at the loading end by side boards 22 (Fig. 3), toward which the sides of the belt are raised by idlers a. Escape of the gaseous treating medium is prevented or restricted by suitable means as by enclosing the main conveyor belt and in fact the entire apparatus in casing 23. The heated gel undergoes syneresis on belt 20, the syneresis water and. condensate from the steam-air mixture running down the belt and dropping off the lower end of the same into sump 24 connected to the sewer. By the time the gel reaches the upper end of belt 20 syneresis is practically complete. As indicated, the gel pieces fall into hopper 25 leading to crushing rolls or other equipment for breaking up the gel pieces, which may then be deposited on belt 26 for movement to subsequent drying and/or washing operations.

The hot gaseous treating medium is supplied to distributing pipes 2l from manifold 21, in turn supplied by one or more mixers or thermo-compressors 28 (Fig. 2). While any suitable gaseous or vaporous medium may be used for heating the gel, steam and air are most convenient, the air being used as a diluent to avoid local overheating of the gel at any point as would be likely to happen if steam alone were discharged directly into the gel. The mixers or thermo-compressors 28 not only adjust the temperature of the gaseous heating medium, but also impose a suitable pressure thereon, as up to 10 to 15 pounds per square inch. A back pressure of about four lbs/sq. in.

at the orifices of the distributing pipes 2| 'is usually sufficient.

Figs. 6 and '7 show a modification in which a narrower conveyor belt 20a is utilized and upon which the gel is heaped hlgherthan is the case with equipment shown in Figs. 1, 2 and 3. To insure thorough heating ofv this deeper mass of gel, the distributing pipes issuing from manifold 21a for the hot gaseous treating medium are provided ori'diilerent levels or at dierent distances from belta. as indicated. One series of distributing pipes 2Ia is shown extending a slight distance above belt '20a and a second series of distributing pipes 2 lb extends parallel to the first series but higher up in the mass of gel and in staggered relation to the pipes ofthe lower series.

`Perforations in the pipes direct the treating fluid in all directions to en'ect thorough and uniform heating of the massof gel.

Fig. 8 shows a diil'erent arrangement in which distributing pipes are omitted and a perforated belt of metal such as link mesh, wire screen, etc. is utilized which will permit the passage therethrough of the treating medium. A chamber 29 of suitable volume and extent is provided immediatelybeneath belt 20h, to which the hot gaseous treating mixture of steam and air is supplied from mixer 28a. Suitable sealing members, such as flaps 30, at the ends and sides of the enclosure forming chamber 29 are provided to prevent the escape vof the treating medium in any direction except upwardly through belt 20h. Chamber 29 is of sumcient extent longitudinally of the belt to insure thorough heating of the entire mass of gel thereon to the desired temperature. A drain (not shown) is arranged for the removal of any syneresis water and condensate which drains through belt 20h into chamber 29.

In Fig. 9 a. vertical mass of gel of any desired height isaccumulated within an enclosure 3| which is supplied at suitable intervals vertically with the treating fluid which may be admitted from annular chambers 32 protected against the entrance of gel by annular guides 33. The enclosure 3| may be continuously fed with gel by one or more mixing heads |3a disposed at the top thereof, and suitable conveying means, such as belt 20c, may be utilized to withdraw the gel from the lower end of enclosure 3| at a rate which will maintain the latter substantially full of gel at all times. Escape of the treating fluid from the belt area may be restricted by a suitable casing 23a.

In the modication of the invention disclosed in Figs. 10, 11 and l2 the use of belts or other types of travelling` conveyors within the heating zone for thev gel is entirely avoided, thus simplifylng the equipment. One or a battery of mixing heads l3b may be provided as desired or required and there may be a preliminary heating of the reactants prior to their entrance into the mixing head by exterior means (not shown) or by extending the enclosure 23h for the gel so as to surround the mixing head (Figs. l0 and 1l) and by coiling the supply lines I 4a, |5a and isa about the mixing head within the enclosure 23h so that the reactant solutions are at least partly heated by the hot treating uid within the enclosure. Enclosure 23h may be of any suitable or desired length and is disposed or inclined at o such an angle that the gel will move therethese openings replaces that lost by condensation within the enclosure 23h and local overheating of the gel, is prevented by bailling the inlets 3B as indicated at 31, so that thesteam is diluted by the air-steam mixture before it hits the gel. Escape of the gaseous treating medium may be suitablyvrestricted or retarded by a flap 38 of flexible material, such as fabric or leather, over the'lower openendof enclosure 23h without interfering with the discharge of the gel therefrom. The enclosure 23h may take the form of a piece of pipe of somewhat larger diameter than the cylinder of gel which issues from the mixing head |317, as indicated in Fig. 1l, or it may be enlarged to accommodate several cylinders of gel in parallelism as indicated in Fig. 12. Either form gives a high degree of ilexibility in the manufacture of the-gel. When the demand is heavy a maximum number of mixing heads may be utilized and as the demand falls oil.7 the number of mixing heads in use may be restricted as desired.

The present invention is particularly advantageous when used in connection with operations designed for a. large output of finished gels. The size and extent oi' the equipment which is required for large scale production is materially decreased if the methods of the present invention are employed. For example, a plant which is preparing as much as a 1,000 lbs/hr. of nished gel must rst manufacture wet gel to the extent of 5,000 to 15,000 lbs/hr. or more since these are the reasonable limits of concentration of solutions of reactants which may be employed to produce gels. This is especially true with gels which contain silica 'as one component. If such large amounts of wet vgel must be accumulated for a suiiicient time to be satisfactorily aged by previous methods, intervals of time as long as six to twenty-four hours must be provided for. This means that in some instances wet or partially dry gel accumulationsI of the order of 100,000 to 200,000 lbs. are necessary at a given instant to obtain aging which will produce satisfactory properties in the iinished dry gel. It is easy to see that the equipment which could keep in continuous process such large masses of material, which at best is handled with diiliculty as far as mechanical and corrosive properties are concerned, requires a large outlay in plant equipment with accompanying high costs. By assuring intimate contact between gaseous media, and especially such media as condense at least in part to give up heat of condensation, such as steam, enables the aging of gel to be carried out with great rapidity. This rapid aging can then be followed by rapid drying without detracting from the good characteristics of the finished product. This means that a plant for the same amount of production may be built with much less equipment and cost. It is necessary, in order to keep the size of drying equipment to a minimum, to dry with reasonable l rapidity. 'I'he preheating described in the present invention allows of drying times of the order of 3 hours or less, even as low as one-half hour to two hours.

We claim as our invention:

1. In a process of producing contact material from inorganic gel, the improvement which comprises forming said gel from reactants, continuously feeding the gel to an ageing zone while said gel is still in the wet condition and before any substantial -ageing has taken place to form a moving bed of gel in said ageing zone and maintaining the. bed of gel at sufficient thickness and temperature to rapidly raise its temperature in the range oi' l202l0 F., moving the gel through the ageing zone to a drying zone at a tempera.- ture within said temperature range and at a rate such that the gel remains in the ageing zone for a sulbstantlal period of at least 10 minutes and not to exceed 2 hours, the gel while moving -through said ageing zone being contacted with an atmosphere of steam and air to maintain the recited temperature'without substantial dehydration of the gel. l

2. In the process of producing contact material from inorganic gel, the improvement which comprises continuously supplying freshly formed gel in wet condition to an ageing zone and moving the gel through said zone at a controlled rate to form a moving layer of substantial depth suiiicient to retain imparted temperature, heating the gel from within the layer to rapidly raise the temperature thereof to within the range of 210 F., retaining the moving layer of gel in an atmosphere of steam and air to maintain the gelat a temperature in the recited range for a substantial period not in excess of two hours to effect ageing of the gel without substantial drying thereof, and continuously withdrawing from the ageing zone liquid formed as a result of syneresis and condensation.

3. En the process of producing Contact mate rial from inorganic gel, the improvement which comprises continuously supplying freshly formed hydrogel in wet condition to a treating zone containing a mixture of steam and air maintaining a temperature of 1Z0-210 F., rapidly heating the hydrogel as supplied to said zone, moving the hydrogel through said zone at a controlled rate to remain in said zone for at least ten minutes and not to exceed two hours and to form a moving bed of substantial thickness suiicient to maintain imparted temperature, the temperature and time of treatment being correlated to effect ageing of the hydrogel to impart improved casting characteristics without reduction in density to an extent impairing settling in subsequent washing.

4. Process for treating inorganic gel which comprises continuously feeding the gel in freshly formed Wet condition to an ageing zone to form a layer of substantial thickness, rapidly heating the gel by conta-ct with heating conduits embedded within the layer to aJ temperature in the range of 1Z0-210 F., continuously moving the layer of gel through an atmosphere of steam and air to maintain the gel at a temperature in the recited range and at a rate and for a time effecting ageing of the gel to an extent suiicient to impart improved casting characteristics Without reduction in density to an extent impairing setn tling in subsequent washing.`

JOHN R. BATES. HUBERT A. SHABAKER. 

